CN102619129A

CN102619129A - Preparation method of high-porosity polymer thin film felt and product prepared according to method

Info

Publication number: CN102619129A
Application number: CN2012101094204A
Authority: CN
Inventors: 杨庆; 郯志清; 沈新元; 吉亚丽; 吴文华
Original assignee: Donghua University
Current assignee: Donghua University
Priority date: 2012-04-13
Filing date: 2012-04-13
Publication date: 2012-08-01
Anticipated expiration: 2032-04-13
Also published as: CN102619129B

Abstract

The invention relates to a preparation method of a high-porosity polymer thin film felt and a product prepared according to the method. The polymer thin film felt adopts a high-porosity film structure formed by stacking flocculent fiber. The preparation method comprises the steps as follows: (1) feeding a proper ratio of polymer raw materials to corresponding solvent to prepare a polymer solution, and preparing a solidifying liquid for a corresponding solution; (2) spraying the polymer solution to the solidifying liquid under high-speed stirring for solidifying to form flocculent fiber suspension; (3) filtering the flocculent fiber suspension, and cleaning with deionized water to obtain flocculent polymer short fiber namely flocculent fiber; (4) dispersing the flocculent fiber in deionized water to form flocculent fiber suspension clear liquid; and (5) fishing out the flocculent fiber from the flocculent fiber suspension clear liquid with a filter gauze to obtain a flocculent fiber thin film felt, and after draining surface moisture, and carrying out deep freezing and sublimation freezing to obtain the high-porosity polymer thin film felt. The thin film felt has better liquid absorption property, and is suitable to be used as a wound dressing; and the preparation method is simple, low in cost and environment friendly.

Description

A kind of high porosity macromolecule membrane felt preparation method and goods thereof

Technical field

The present invention relates to a kind of high porosity macromolecule membrane felt preparation method and goods thereof.

Background technology

In liquid, to be made into the film felt be a kind of method commonly used with copying the paper method then with the fiber uniformly dispersing.People such as Wei Yuezhen [Wei Yuezhen etc.; A kind of paper made from mixed pulp of grass and synthetic fibre; 89106114.2] invented and a kind ofly be mixed and made into a kind of method of copying paper of mixing with dogstail slurry and synthetic fiber; The adding of synthetic fiber has significantly improved the intensity and the toughness of grass pulp paper, has improved the value class of dogstail.People such as Zhang Xingxian [Zhang Xingxian etc.; A kind of process of copying paper production asbestos yarn with asbestos short fibre; 94110411.7] invented a kind of process of using asbestos short fibre after copying paper, to produce asbestos yarn as raw material; Earlier asbestos short fibre is added after the water making beating and remove impurity through purification and form and to copy paper pulp; Adopt paper technology again and process asbestos fibre wet paper, then l Water Paper is pushed or vacuum dehydration handles after roller shape asbestos fibre paper roll is processed in oven dry through adding nonwoven fabric or filament fiber.The little Wal of American special B Xi Er [the special B Xi Er in little Wal etc.; Use the papermaking process of enzyme and polymer composition; 00815720.0] in paper making pulp, introduce at least a cellulolytic enzyme composition and at least a cationic polymer compositions simultaneously to form treated paper pulp, this paper pulp can be made into paper.

The above-mentioned resulting film felt of this type papermaking process of introducing (film paper) all adopts and dries in the shade or drying mode removal moisture, and dried film paper structure is tight, and mechanical strength increases.But from another point of view, this type film paper voidage is lower, so moisture pick-up properties is lower, is inappropriate for that be applied in need be than the occasion of high absorption property.

Summary of the invention

The purpose of this invention is to provide a kind of high porosity macromolecule membrane felt preparation method and goods thereof, this film felt is the high voidage membrane structure that the wadding fibrous accumulation of macromolecule forms, and its solution absorbs property is good, can be used for the treatment of human body surface wound; And the preparation method is simple, is suitable for suitability for industrialized production.

A kind of high porosity macromolecule membrane felt preparation method of the present invention may further comprise the steps:

(1) macromolecule raw material of an amount of ratio is invested in processes Polymer Solution in the corresponding solvent; Allocate the solidification liquid of corresponding Polymer Solution;

(2) under high-speed stirred, spray Polymer Solution, make it be frozen into the fine suspension of wadding to solidification liquid; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

(3) the fine suspension of wadding a quilt with cotton is filtered, clean, obtain the cotton-shaped polymeric staple fiber fibre of promptly wadding a quilt with cotton with deionized water;

(4) fibre of will wadding a quilt with cotton again is dispersed in the deionized water and forms the fine suspension clear liquid of wadding, and its concentration is 0.1～5 (W/W) %;

(5) the wadding fibre that will wad a quilt with cotton in the fine suspension clear liquid with filter screen is taken up, and obtains one deck by the fine film felt that forms of wadding;

(6) behind the dried surface moisture of film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, transfer to then and in the freeze drying box it is distilled freezingly, obtain high porosity macromolecule membrane felt.

As optimized technical scheme:

Aforesaid a kind of high porosity macromolecule membrane felt preparation method, described macromolecule raw material is polycaprolactone, polyethylene glycol, polytetramethylene carbonate diol, PLA, cellulose, collagen, shitosan or sodium alginate/sodium carboxymethylcellulose; Described coordinative solvent and the mass concentration of processing Polymer Solution are: for polycaprolactone, solvent is an oxolane, and concentration is 3～30% (W/W) %; For polyethylene glycol, molecular weight is 2000～20000, and solvent is 75 ℃ of hot water, and concentration is 3～30% (W/W) %; For polytetramethylene carbonate diol, solvent is a dimethyl formamide, and concentration is 3～30 (W/W) %; For PLA, solvent is a carrene, and concentration is 3～30 (W/W) %; For cellulose, solvent is 4-methyl morpholine-N-oxide, and concentration is 1～10 (W/W) %; For collagen, solvent is 80 ± 5 ℃ of hot water, and concentration is 3～30 (W/W) %; For shitosan, solvent is acetic acid (1～3 (W/W) %), and concentration is 0.5～4 (W/W) %; For sodium alginate/sodium carboxymethylcellulose, solvent is a deionized water, and concentration is 3.6 (W/W) %.Select for use above-mentioned macromolecular material to want several considerations: at first wanting to dissolve becomes solution; Secondly solvent is also preferably environmentally friendly; The recovery of solvent also is a Consideration in addition.

Aforesaid a kind of high porosity macromolecule membrane felt preparation method, described solidification liquid is allocated as: for polycaprolactone/tetrahydrofuran solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For polyethylene glycol/75 ± 5 ℃ aqueous solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For polytetramethylene carbonate diol/dimethyl formamide solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For PLA/dichloromethane solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For cellulose/4-methyl morpholine-N-oxide solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For collagen, the solidification liquid allocation process is: sodium sulphate and aluminum sulfate are added 25 ± 2 ℃ of deionized waters stir and dissolve, the control addition promptly gets sodium sulphate and the aluminum sulfate solubility that reaches capacity; For shitosan/acetum; NaOH in the solidification liquid: urea: zinc acetate=5 ± 0.5: 05 ± 0.1: 0.5 ± 0.1; Solidification liquid concentration is 6 ± 0.7 (W/W) %, gets stirring in NaOH, urea and 25 ± 2 ℃ of deionized waters of zinc acetate input during allotment; For sodium alginate/carboxymethylcellulose sodium solution, solidification liquid is the calcium chloride water of 3.5 ± 0.5 (W/W) %, during allotment calcium chloride is dropped in proportion to stir in 25 ± 2 ℃ of deionized waters.When selecting for use macromolecular material to process solution, also will consider solidification liquid, solidification liquid is just not too suitable to the disagreeableness words of environment, will consider the recovery problem of solidification liquid in addition.

Aforesaid a kind of high porosity macromolecule membrane felt preparation method, it is 100～1000rpm that described high-speed stirred refers to the speed of agitator interval; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine, open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.2～0.3l/min with vaporific form.Spraying whipping process has very big influence to the fine pattern of wadding a quilt with cotton, and as a rule mixing speed is fast more, and the wadding of formation is fine just fine and closely woven more; Slow like mixing speed, the fine structure of the wadding that then obtains is comparatively coarse.

Aforesaid a kind of high porosity macromolecule membrane felt preparation method; Described filter operation is: the Buchner funnel that will lay filter paper earlier is inserted in Bu Shi flask top opening and with sealing joint; To spray the fine suspension of wadding of solidification forming then and pour Buchner funnel into; Suspension is drawn into beaker under suction function, the fine solid of wadding a quilt with cotton is stayed in the Buchner funnel; Described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Through repeatedly filtration with disperse the coagulating agent in can the original solution of flush away, fine suspension clear liquid obtains wadding a quilt with cotton.Cleaning process is comparatively simple, and main purpose is the solvent in the flush away wadding fibre, and the retaining of solvent can influence the final result of use of product.

Aforesaid a kind of high porosity macromolecule membrane felt preparation method, described filter screen is a kind of diddle-net that paper is used of copying, and the filter screen material is a stainless steel, and mesh size is 200～400 orders; Described cryogenic refrigeration is meant and sample is refrigerated to-40～-50 ℃ that the moisture content that contains has become ice cube; Described distillation is freezing to be carried out in vacuum freeze drier, and the distillation refrigerating process is: freeze-drying time is 48 ± 2 hours, freeze-drying pressure 80 ± 5Pa, 60 ± 2 ℃ of temperature of heating plate.Copy that paper filter is done, the distillation refrigerating process has considerable influence to the porosity of film felt, filter the fine volume of overdrying wadding and just dwindle, the moisture in the wadding fibre is just few, and the porosity of final film felt is just little, so the fine moisture percentage of control wadding can be controlled the porosity of film felt.

The present invention also provides a kind of high porosity macromolecule membrane felt preparation method, will be set by step two or more the fine suspension clear liquid of the wadding blend that makes of (1)～(4), (5) then set by step～(6) operation obtains the polymer blended film felt of high porosity.The blend proportioning can be arbitrary proportion.

The goods that the present invention provides a kind of aforesaid high porosity macromolecule membrane felt preparation method to make again, described goods are high porosity macromolecule membrane felt, pile up the high voidage membrane structure that forms for cotton-shaped polymeric staple fiber; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula; The voidage of described high porosity macromolecule membrane felt is 30～80 (V/V) %.

Aforesaid goods, described macromolecule are one or more the combination in polycaprolactone, polyethylene glycol, polytetramethylene carbonate diol, PLA, cellulose, collagen, shitosan, the sodium alginate/sodium carboxymethylcellulose; Described membrane structure is the connectivity structure with high porosity.

Traditional paper method of copying is exactly the short fiber in the pulp liquor evenly to be taken up form the film felt, in dry run after this, adopts nature to dry in the shade usually or the method for drying removal moisture.Employing is dried in the shade or to shine the paper compactness that drying method obtains better, and paper strength is also higher.The polymer blended film felt that the present invention produces is had relatively high expectations to performance of keeping humidity, therefore hopes that the film felt has higher porosity to absorb water.If adopt common drying means, along with the evaporation of moisture, the micropore in the original structure of paper (or film) is tending towards dwindling and even disappearing under external pressure, and it is fine and close more that overall structure becomes.And the present invention adopts freeze-drying to remove moisture, and in water sublimed, those apertures are still remained stationary.Like this, final finished has the high porosity structure, helps adsorbing more water.Through retrieval, do not see to have and carry out cryodesiccated document copying the paper paper.

Experiment showed, that the wadding fibrous film felt after freeze drying is handled has strength and elongation preferably, maximum characteristics are that voidage is high, and absorbency is good, is well suited for as wound dressing.

Beneficial effect:

(1) macromolecule membrane felt of the present invention is the high-voidage membrane structure that forms with wadding fibrous accumulation, and the final products of gained after its freeze drying are had high porosity and pick up.

(2) to have strength and elongation preferably, particularly absorbency good for high voidage macromolecule membrane felt of the present invention, is well suited for as wound dressing.Its preparation method is simple, and cost is low, and is environmentally friendly, and economic benefit is high.

The specific embodiment

Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.

Embodiment 1

A kind of high porosity macromolecule membrane felt preparation method may further comprise the steps:

(1) polycaprolactone is invested in processes the Polymer Solution that concentration is 3% (W/W) % in the oxolane; Solidification liquid is 25 ℃ of deionized waters;

(2), the rotating speed of 100rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.2l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

(3) the fine suspension of wadding a quilt with cotton is filtered; The Buchner funnel that to lay filter paper earlier is inserted in Bu Shi flask top opening and with sealing joint; To spray the fine suspension of wadding of solidification forming then and pour Buchner funnel into, suspension is drawn into beaker under suction function, and the fine solid of wadding a quilt with cotton is stayed in the Buchner funnel; Clean with deionized water, obtain the cotton-shaped polymeric staple fiber fibre of promptly wadding a quilt with cotton;

(4) fibre of will wadding a quilt with cotton again is dispersed in the deionized water and forms the fine suspension clear liquid of wadding, and described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Its concentration is 0.1 (W/W) %;

(5) the wadding fibre that will wad a quilt with cotton in the fine suspension clear liquid with filter screen is taken up, and obtains one deck by the fine film felt that forms of wadding; Described filter screen is a kind of diddle-net that paper is used of copying, and the filter screen material is a stainless steel, and mesh size is 200 orders;

(6) behind the dried surface moisture of film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, described cryogenic refrigeration is meant and sample is refrigerated to-40 ℃ that the moisture content that contains has become ice cube; Transfer to then it is distilled in the freeze drying box freezing; The distillation refrigerating process is: freeze-drying time is 46 hours; Freeze-drying pressure 75Pa; 58 ℃ of temperature of heating plate, obtaining voidage is the high porosity macromolecule membrane felt of 30 (V/V) %, is also promptly piled up the high porosity polycaprolactone film felt of the high voidage membrane structure that forms by cotton-shaped polycaprolactone short fiber.

Embodiment 2

(1) polycaprolactone is invested in processes the Polymer Solution that concentration is 30% (W/W) % in the oxolane; Solidification liquid is 23 ℃ of deionized waters;

(2), the rotating speed of 1000rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.3l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

(4) fibre of will wadding a quilt with cotton again is dispersed in the deionized water and forms the fine suspension clear liquid of wadding, and described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Its concentration is 2 (W/W) %;

(5) the wadding fibre that will wad a quilt with cotton in the fine suspension clear liquid with filter screen is taken up, and obtains one deck by the fine film felt that forms of wadding; Described filter screen is a kind of diddle-net that paper is used of copying, and the filter screen material is a stainless steel, and mesh size is 400 orders;

(6) behind the dried surface moisture of film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, described cryogenic refrigeration is meant and sample is refrigerated to-50 ℃ that the moisture content that contains has become ice cube; Transfer to then it is distilled in the freeze drying box freezing; The distillation refrigerating process is: freeze-drying time is 46 hours; Freeze-drying pressure 75Pa; 58 ℃ of temperature of heating plate, obtaining voidage is the high porosity macromolecule membrane felt of 30 (V/V) %, is also promptly piled up the high porosity polycaprolactone film felt of the high voidage membrane structure that forms by cotton-shaped polycaprolactone short fiber.

Embodiment 3

(1) polycaprolactone is invested in processes the Polymer Solution that concentration is 15% (W/W) % in the oxolane; Solidification liquid is 27 ℃ of deionized waters;

(2), the rotating speed of 500rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.24l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

(4) fibre of will wadding a quilt with cotton again is dispersed in the deionized water and forms the fine suspension clear liquid of wadding, and described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Its concentration is 5 (W/W) %;

(6) behind the dried surface moisture of film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, described cryogenic refrigeration is meant and sample is refrigerated to-45 ℃ that the moisture content that contains has become ice cube; Transfer to then it is distilled in the freeze drying box freezing; The distillation refrigerating process is: freeze-drying time is 46 hours; Freeze-drying pressure 75Pa; 58 ℃ of temperature of heating plate, obtaining voidage is the high porosity macromolecule membrane felt of 30 (V/V) %, is also promptly piled up the high porosity polycaprolactone film felt of the high voidage membrane structure that forms by cotton-shaped polycaprolactone short fiber.

Embodiment 4

(1) be that 20000 polyethylene glycol is invested in and processes the Polymer Solution that concentration is 3% (W/W) % in 80 ℃ of hot water with molecular weight; Solidification liquid is 25 ℃ of deionized waters;

(2), the rotating speed of 100rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.3l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

(6) behind the dried surface moisture of film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, described cryogenic refrigeration is meant and sample is refrigerated to-50 ℃ that the moisture content that contains has become ice cube; Transfer to then it is distilled in the freeze drying box freezing; The distillation refrigerating process is: freeze-drying time is 50 hours; Freeze-drying pressure 85Pa; 62 ℃ of temperature of heating plate, obtaining voidage is the high porosity macromolecule membrane felt of 80 (V/V) %, is also promptly piled up the high porosity polyethylene glycol film felt of the high voidage membrane structure that forms by cotton-shaped polyethylene glycol short fiber.

Embodiment 5

(1) be that 20000 polyethylene glycol is invested in and processes the Polymer Solution that concentration is 30% (W/W) % in 80 ℃ of hot water with molecular weight; Solidification liquid is 25 ℃ of deionized waters;

Embodiment 6

(1) be that 20000 polyethylene glycol is invested in and processes the Polymer Solution that concentration is 16% (W/W) % in 80 ℃ of hot water with molecular weight; Solidification liquid is 25 ℃ of deionized waters;

(2), the rotating speed of 600rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.3l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 7

(1) polytetramethylene carbonate diol is invested in processes the Polymer Solution that concentration is 3% (W/W) % in the dimethyl formamide; Solidification liquid is 25 ℃ of deionized waters;

(2), the rotating speed of 100rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.21l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

(4) fibre of will wadding a quilt with cotton again is dispersed in the deionized water and forms the fine suspension clear liquid of wadding, and described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Its concentration is 0.2 (W/W) %;

(5) the wadding fibre that will wad a quilt with cotton in the fine suspension clear liquid with filter screen is taken up, and obtains one deck by the fine film felt that forms of wadding; Described filter screen is a kind of diddle-net that paper is used of copying, and the filter screen material is a stainless steel, and mesh size is 300 orders;

(6) behind the dried surface moisture of film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, described cryogenic refrigeration is meant and sample is refrigerated to-45 ℃ that the moisture content that contains has become ice cube; Transfer to then it is distilled in the freeze drying box freezing; The distillation refrigerating process is: freeze-drying time is 48 hours; Freeze-drying pressure 80Pa; 60 ℃ of temperature of heating plate, obtaining voidage is the high porosity macromolecule membrane felt of 55 (V/V) %, is also promptly piled up the high porosity polytetramethylene carbonate diol film felt of the high voidage membrane structure that forms by cotton-shaped polytetramethylene carbonate diol short fiber.

Embodiment 8

(1) polytetramethylene carbonate diol is invested in processes the Polymer Solution that concentration is 30% (W/W) % in the dimethyl formamide; Solidification liquid is 25 ℃ of deionized waters;

(2), the rotating speed of 1000rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.21l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 9

(1) polytetramethylene carbonate diol is invested in processes the Polymer Solution that concentration is 10% (W/W) % in the dimethyl formamide; Solidification liquid is 25 ℃ of deionized waters;

(2), the rotating speed of 400rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.21l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 10

(1) PLA is invested in processes the Polymer Solution that concentration is 3% (W/W) % in the carrene; Solidification liquid is 25 ℃ of deionized waters;

(2), the rotating speed of 100rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.22l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

(5) the wadding fibre that will wad a quilt with cotton in the fine suspension clear liquid with filter screen is taken up, and obtains one deck by the fine film felt that forms of wadding; Described filter screen is a kind of diddle-net that paper is used of copying, and the filter screen material is a stainless steel, and mesh size is 250 orders;

(6) behind the dried surface moisture of film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, described cryogenic refrigeration is meant and sample is refrigerated to-42 ℃ that the moisture content that contains has become ice cube; Transfer to then it is distilled in the freeze drying box freezing; The distillation refrigerating process is: freeze-drying time is 47 hours; Freeze-drying pressure 78Pa; 59 ℃ of temperature of heating plate, obtaining voidage is the high porosity macromolecule membrane felt of 40 (V/V) %, is also promptly piled up the high porosity polylactic acid film felt of the high voidage membrane structure that forms by cotton-shaped PLA short fiber.

Embodiment 11

(1) PLA is invested in processes the Polymer Solution that concentration is 30% (W/W) % in the carrene; Solidification liquid is 25 ℃ of deionized waters;

(2), the rotating speed of 1000rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.22l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 12

(1) PLA is invested in processes the Polymer Solution that concentration is 11% (W/W) % in the carrene; Solidification liquid is 25 ℃ of deionized waters;

(2), the rotating speed of 400rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.22l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 13

(1) cellulose is invested in processes the Polymer Solution that concentration is 1% (W/W) % in 4-methyl morpholine-N-oxide; Solidification liquid is 25 ℃ of deionized waters;

(2), the rotating speed of 100rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.24l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

(4) fibre of will wadding a quilt with cotton again is dispersed in the deionized water and forms the fine suspension clear liquid of wadding, and described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Its concentration is 0.15 (W/W) %;

(5) the wadding fibre that will wad a quilt with cotton in the fine suspension clear liquid with filter screen is taken up, and obtains one deck by the fine film felt that forms of wadding; Described filter screen is a kind of diddle-net that paper is used of copying, and the filter screen material is a stainless steel, and mesh size is 350 orders;

(6) behind the dried surface moisture of film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, described cryogenic refrigeration is meant and sample is refrigerated to-44 ℃ that the moisture content that contains has become ice cube; Transfer to then it is distilled in the freeze drying box freezing; The distillation refrigerating process is: freeze-drying time is 48 hours; Freeze-drying pressure 82Pa; 61 ℃ of temperature of heating plate, obtaining voidage is the high porosity macromolecule membrane felt of 50 (V/V) %, also promptly piles up the high porosity cellophane felt of the high voidage membrane structure that forms by wadding fibrous plain short fiber.

Embodiment 14

(1) cellulose is invested in processes the Polymer Solution that concentration is 10% (W/W) % in 4-methyl morpholine-N-oxide; Solidification liquid is 25 ℃ of deionized waters;

(2), the rotating speed of 1000rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.24l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 15

(1) cellulose is invested in processes the Polymer Solution that concentration is 5% (W/W) % in 4-methyl morpholine-N-oxide; Solidification liquid is 25 ℃ of deionized waters;

(2), the rotating speed of 400rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.24l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 16

(1) collagen is invested in 85 ℃ the hot water processes the Polymer Solution that concentration is 3% (W/W) %; Solidification liquid is sodium sulphate and aluminum sulfate saturated solution;

(2), the rotating speed of 100rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.25/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

(6) behind the dried surface moisture of film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, described cryogenic refrigeration is meant and sample is refrigerated to-46 ℃ that the moisture content that contains has become ice cube; Transfer to then it is distilled in the freeze drying box freezing; The distillation refrigerating process is: freeze-drying time is 48 hours; Freeze-drying pressure 80Pa; 60 ℃ of temperature of heating plate, obtaining voidage is the high porosity macromolecule membrane felt of 60 (V/V) %, is also promptly piled up the high porosity collagen film felt of the high voidage membrane structure that forms by cotton-shaped collagen short fiber.

Embodiment 17

(1) collagen is invested in 85 ℃ the hot water processes the Polymer Solution that concentration is 30% (W/W) %; Solidification liquid is sodium sulphate and aluminum sulfate saturated solution;

(2), the rotating speed of 1000rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.25/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 18

(1) collagen is invested in 85 ℃ the hot water processes the Polymer Solution that concentration is 12% (W/W) %; Solidification liquid is sodium sulphate and aluminum sulfate saturated solution;

(2), the rotating speed of 500rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.25/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 19

(1) shitosan is invested in the acetum of 3 (W/W) % processes the Polymer Solution that concentration is 0.5% (W/W) %; Solidification liquid is the mixed solution of NaOH, urea and zinc acetate, NaOH: urea: the mass ratio of zinc acetate=5: 05: 0.5, solidification liquid concentration are 6 (W/W) %;

(2), the rotating speed of 100rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.26l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

(4) fibre of will wadding a quilt with cotton again is dispersed in the deionized water and forms the fine suspension clear liquid of wadding, and described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Its concentration is 0.12 (W/W) %;

(6) behind the dried surface moisture of film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, described cryogenic refrigeration is meant and sample is refrigerated to-48 ℃ that the moisture content that contains has become ice cube; Transfer to then it is distilled in the freeze drying box freezing; The distillation refrigerating process is: freeze-drying time is 49 hours; Freeze-drying pressure 78Pa; 61 ℃ of temperature of heating plate, obtaining voidage is the high porosity macromolecule membrane felt of 70 (V/V) %, is also promptly piled up the high porosity shitosan film felt of the high voidage membrane structure that forms by cotton-shaped shitosan short fiber.

Embodiment 20

(1) shitosan is invested in the acetum of 3 (W/W) % processes the Polymer Solution that concentration is 4% (W/W) %; Solidification liquid is the mixed solution of NaOH, urea and zinc acetate, NaOH: urea: the mass ratio of zinc acetate=5: 05: 0.5, solidification liquid concentration are 6 (W/W) %;

(2), the rotating speed of 1000rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.26l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 21

(1) shitosan is invested in the acetum of 3 (W/W) % processes the Polymer Solution that concentration is 2% (W/W) %; Solidification liquid is the mixed solution of NaOH, urea and zinc acetate, NaOH: urea: the mass ratio of zinc acetate=5: 05: 0.5, solidification liquid concentration are 6 (W/W) %;

(2), the rotating speed of 600rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.26l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 22

(1) sodium alginate/sodium carboxymethylcellulose is invested in processes the Polymer Solution that concentration is 3.4% (W/W) % in the deionized water; Solidification liquid is the calcium chloride water of 4.0 (W/W) %;

(2), the rotating speed of 100rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.27l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

(6) behind the dried surface moisture of film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, described cryogenic refrigeration is meant and sample is refrigerated to-45 ℃ that the moisture content that contains has become ice cube; Transfer to then it is distilled in the freeze drying box freezing; The distillation refrigerating process is: freeze-drying time is 46 hours; Freeze-drying pressure 80Pa; 60 ℃ of temperature of heating plate, obtaining voidage is the high porosity macromolecule membrane felt of 55 (V/V) %, is also promptly piled up the high porosity sodium alginate/carboxymethyl cellulose film felt of the high voidage membrane structure that forms by cotton-shaped sodium alginate/carboxymethyl cellulose short fiber.

Embodiment 23

(1) sodium alginate/sodium carboxymethylcellulose is invested in processes the Polymer Solution that concentration is 3.8% (W/W) % in the deionized water; Solidification liquid is the calcium chloride water of 4.0 (W/W) %;

(2), the rotating speed of 1000rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.27l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 24

(1) sodium alginate/sodium carboxymethylcellulose is invested in processes the Polymer Solution that concentration is 3.6% (W/W) % in the deionized water; Solidification liquid is the calcium chloride water of 4.0 (W/W) %;

(2), the rotating speed of 500rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.27l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula;

Embodiment 25

The two component blend macromolecule membrane felt preparation methods of a kind of high porosity polycaprolactone and polyethylene glycol may further comprise the steps:

(1) polycaprolactone is invested in processes the Polymer Solution that concentration is 3% (W/W) % in the oxolane; Solidification liquid is 25 ℃ of deionized waters; , the rotating speed of 100rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.2l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula; Fine suspension filters to wadding a quilt with cotton; The Buchner funnel that to lay filter paper earlier is inserted in Bu Shi flask top opening and with sealing joint; To spray the fine suspension of wadding of solidification forming then and pour Buchner funnel into, suspension is drawn into beaker under suction function, and the fine solid of wadding a quilt with cotton is stayed in the Buchner funnel; Clean with deionized water, obtain the cotton-shaped polymeric staple fiber fibre of promptly wadding a quilt with cotton; The fibre of will wadding a quilt with cotton again is dispersed in and forms the fine suspension clear liquid of wadding in the deionized water, and described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Its concentration is 0.1 (W/W) %;

(2) be that 20000 polyethylene glycol is invested in and processes the Polymer Solution that concentration is 30% (W/W) % in 80 ℃ of hot water with molecular weight; Solidification liquid is 25 ℃ of deionized waters; , the rotating speed of 1000rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.3l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula; Fine suspension filters to wadding a quilt with cotton; The Buchner funnel that to lay filter paper earlier is inserted in Bu Shi flask top opening and with sealing joint; To spray the fine suspension of wadding of solidification forming then and pour Buchner funnel into, suspension is drawn into beaker under suction function, and the fine solid of wadding a quilt with cotton is stayed in the Buchner funnel; Clean with deionized water, obtain the cotton-shaped polymeric staple fiber fibre of promptly wadding a quilt with cotton; The fibre of will wadding a quilt with cotton again is dispersed in and forms the fine suspension clear liquid of wadding in the deionized water, and described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Its concentration is 0.1 (W/W) %;

(3) polycaprolactone fine suspension clear liquid and the polyethylene glycol fine suspension clear liquid of wadding a quilt with cotton of wadding a quilt with cotton is evenly mixed with 1: 1 ratio; Blend wadding fibre with filter screen will mix in the fine suspension clear liquid of wadding is taken up, and obtains one deck by the fine film felt that forms of blend wadding; Described filter screen is a kind of diddle-net that paper is used of copying, and the filter screen material is a stainless steel, and mesh size is 200 orders;

(4) behind the dried surface moisture of blend film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, described cryogenic refrigeration is meant and sample is refrigerated to-40 ℃ that the moisture content that contains has become ice cube; Transfer to then it is distilled in the freeze drying box freezing; The distillation refrigerating process is: freeze-drying time is 46 hours; Freeze-drying pressure 75Pa; 58 ℃ of temperature of heating plate, obtaining voidage is the polymer blended film felt of high porosity of 30 (V/V) %, is also promptly piled the high porosity polycaprolactone and the polyethylene glycol blending film felt of the high voidage membrane structure that mixed-stacking forms by cotton-shaped polycaprolactone short fiber heap and polyethylene glycol short fiber.

Embodiment 26

A kind of high porosity polytetramethylene carbonate diol, PLA and cellulose iii component blend macromolecule membrane felt preparation method may further comprise the steps:

(1) polytetramethylene carbonate diol is invested in processes the Polymer Solution that concentration is 10% (W/W) % in the dimethyl formamide; Solidification liquid is 25 ℃ of deionized waters; , the rotating speed of 200rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.21l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula; Fine suspension filters to wadding a quilt with cotton; The Buchner funnel that to lay filter paper earlier is inserted in Bu Shi flask top opening and with sealing joint; To spray the fine suspension of wadding of solidification forming then and pour Buchner funnel into, suspension is drawn into beaker under suction function, and the fine solid of wadding a quilt with cotton is stayed in the Buchner funnel; Clean with deionized water, obtain the cotton-shaped polymeric staple fiber fibre of promptly wadding a quilt with cotton; The fibre of will wadding a quilt with cotton again is dispersed in and forms the fine suspension clear liquid of wadding in the deionized water, and described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Its concentration is 0.2 (W/W) %;

(2) PLA is invested in processes the Polymer Solution that concentration is 3% (W/W) % in the carrene; Solidification liquid is 25 ℃ of deionized waters; , the rotating speed of 300rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.22l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula; Fine suspension filters to wadding a quilt with cotton; The Buchner funnel that to lay filter paper earlier is inserted in Bu Shi flask top opening and with sealing joint; To spray the fine suspension of wadding of solidification forming then and pour Buchner funnel into, suspension is drawn into beaker under suction function, and the fine solid of wadding a quilt with cotton is stayed in the Buchner funnel; Clean with deionized water, obtain the cotton-shaped polymeric staple fiber fibre of promptly wadding a quilt with cotton; The fibre of will wadding a quilt with cotton again is dispersed in and forms the fine suspension clear liquid of wadding in the deionized water, and described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Its concentration is 0.2 (W/W) %;

(3) cellulose is invested in processes the Polymer Solution that concentration is 1% (W/W) % in 4-methyl morpholine-N-oxide; Solidification liquid is 25 ℃ of deionized waters; , the rotating speed of 400rpm sprays Polymer Solution under stirring to solidification liquid; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine; Open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.24l/min with vaporific form, make it be frozen into the fine suspension of wadding; The fine suspension of described wadding is made up of cotton-shaped polymeric staple fiber and suspension, and described cotton-shaped polymeric staple fiber is suspended in the suspension; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula; Fine suspension filters to wadding a quilt with cotton; The Buchner funnel that to lay filter paper earlier is inserted in Bu Shi flask top opening and with sealing joint; To spray the fine suspension of wadding of solidification forming then and pour Buchner funnel into, suspension is drawn into beaker under suction function, and the fine solid of wadding a quilt with cotton is stayed in the Buchner funnel; Clean with deionized water, obtain the cotton-shaped polymeric staple fiber fibre of promptly wadding a quilt with cotton; The fibre of will wadding a quilt with cotton again is dispersed in and forms the fine suspension clear liquid of wadding in the deionized water, and described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Its concentration is 0.2 (W/W) %;

(4) polytetramethylene carbonate diol wad a quilt with cotton fine suspension clear liquid and the fine suspension clear liquid of cellulose wadding of fine suspension clear liquid, PLA of wadding a quilt with cotton evenly mixed with 1: 1: 1 ratio; Three component blend wadding fibre with filter screen will mix in the fine suspension clear liquid of wadding is taken up, and obtains one deck by the fine film felt that forms of three component blend wadding; Described filter screen is a kind of diddle-net that paper is used of copying, and the filter screen material is a stainless steel, and mesh size is: 300 orders;

(5) behind the dried surface moisture of three component blend film felt filter to be taken up, put into refrigerator and carry out cryogenic refrigeration, described cryogenic refrigeration is meant and sample is refrigerated to-50 ℃ that the moisture content that contains has become ice cube; Transfer to then it is distilled in the freeze drying box freezing; The distillation refrigerating process is: freeze-drying time is 50 hours; Freeze-drying pressure 80Pa; 62 ℃ of temperature of heating plate, obtaining voidage is the high porosity macromolecule three component blend film felts of 50 (V/V) %, high porosity polytetramethylene carbonate diol, PLA and the cellulose iii component blend film felt of the high voidage membrane structure that is also promptly formed by cotton-shaped polytetramethylene carbonate diol short fiber heap, polylactic acid short-fiber and cellulose fluff heap mixed-stacking.

Claims

1. high porosity macromolecule membrane felt preparation method is characterized in that may further comprise the steps:

(6) carry out cryogenic refrigeration behind the dried surface moisture of film felt filter to be taken up, it is freezing then it to be distilled, and obtains high porosity macromolecule membrane felt.

2. a kind of high porosity macromolecule membrane felt preparation method according to claim 1; It is characterized in that described macromolecule raw material is polycaprolactone, polyethylene glycol, polytetramethylene carbonate diol, PLA, cellulose, collagen, shitosan or sodium alginate/sodium carboxymethylcellulose; Described coordinative solvent and the mass concentration of processing Polymer Solution are: for polycaprolactone, solvent is an oxolane, and concentration is 3～30% (W/W) %; For polyethylene glycol, molecular weight is 2000～20000, and solvent is 75 ± 5 ℃ of hot water, and concentration is 3～30% (W/W) %; For polytetramethylene carbonate diol, solvent is a dimethyl formamide, and concentration is 3～30 (W/W) %; For PLA, solvent is a carrene, and concentration is 3～30 (W/W) %; For cellulose, solvent is 4-methyl morpholine-N-oxide, and concentration is 1～10 (W/W) %; For collagen, solvent is 80 ± 5 ℃ of hot water, and concentration is 3～30 (W/W) %; For shitosan, solvent is acetic acid (1～3 (W/W) %), and concentration is 0.5～4 (W/W) %; For sodium alginate/sodium carboxymethylcellulose, solvent is a deionized water, and concentration is 3.6 ± 0.2 (W/W) %.

3. a kind of high porosity macromolecule membrane felt preparation method according to claim 1 is characterized in that described solidification liquid is allocated as: for polycaprolactone/tetrahydrofuran solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For polyethylene glycol/75 ± 5 ℃ aqueous solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For polytetramethylene carbonate diol/dimethyl formamide solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For PLA/dichloromethane solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For cellulose/4-methyl morpholine-N-oxide solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For collagen, the solidification liquid allocation process is: sodium sulphate and aluminum sulfate are added 25 ± 2 ℃ of deionized waters stir and dissolve, the control addition promptly gets sodium sulphate and the aluminum sulfate solubility that reaches capacity; For shitosan/acetum; NaOH in the solidification liquid: urea: the mass ratio of zinc acetate=5 ± 0.5: 05 ± 0.1: 0.5 ± 0.1; Solidification liquid concentration is 6 ± 0.7 (W/W) %, gets stirring in NaOH, urea and 25 ± 2 ℃ of deionized waters of zinc acetate input during allotment; For sodium alginate/carboxymethylcellulose sodium solution, solidification liquid is the calcium chloride water of 3.5 ± 0.5 (W/W) %, during allotment calcium chloride is dropped in proportion to stir in 25 ± 2 ℃ of deionized waters.

4. a kind of high porosity macromolecule membrane felt preparation method according to claim 1 is characterized in that it is 100～1000rpm that described high-speed stirred refers to the speed of agitator interval; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine, open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.2～0.3l/min with vaporific form.

5. a kind of high porosity macromolecule membrane felt preparation method according to claim 1; It is characterized in that; Described filter operation is: the Buchner funnel that will lay filter paper earlier is inserted in Bu Shi flask top opening and with sealing joint; To spray the fine suspension of wadding of solidification forming then and pour Buchner funnel into, suspension is drawn into beaker under suction function, and the fine solid of wadding a quilt with cotton is stayed in the Buchner funnel; Described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Through repeatedly filtration with disperse the coagulating agent in can the original solution of flush away, fine suspension clear liquid obtains wadding a quilt with cotton.

6. a kind of high porosity macromolecule membrane felt preparation method according to claim 1 is characterized in that described filter screen is a kind of diddle-net that paper is used of copying, and the filter screen material is a stainless steel, and mesh size is 200～400 orders; Described cryogenic refrigeration is meant and sample is refrigerated to-40～-50 ℃ that the moisture content that contains has become ice cube; Described distillation is freezing to be carried out in vacuum freeze drier, and the distillation refrigerating process is: freeze-drying time is 48 ± 2 hours, freeze-drying pressure 80 ± 5Pa, 60 ± 2 ℃ of temperature of heating plate.

7. a kind of high porosity macromolecule membrane felt preparation method as claimed in claim 1; It is characterized in that: will be set by step two or more the fine suspension clear liquid of the wadding blend that makes of (1)～(4), (5) then set by step～(6) operation obtains the polymer blended film felt of high porosity.

8. the goods that make like claim 1 or 7 described a kind of high porosity macromolecule membrane felt preparation methods, it is characterized in that: described goods are high porosity macromolecule membrane felt, pile up the high voidage membrane structure that forms for cotton-shaped polymeric staple fiber; Described cotton-shaped polymeric staple fiber is meant little and loose polymeric staple fiber coagula; The voidage of described high porosity macromolecule membrane felt is 30～80 (V/V) %.

9. goods according to claim 8; It is characterized in that described macromolecule is one or more the combination in polycaprolactone, polyethylene glycol, polytetramethylene carbonate diol, PLA, cellulose, collagen, shitosan, the sodium alginate/sodium carboxymethylcellulose; Described membrane structure is the connectivity structure with high porosity.